Separation of closely boiling fractions from a binary mixture



aeeaese with a liquid phase in the lower portion of the amount of heat to be removed from the overstream from the lower portion of the column,

withdrawing an ethylene stream from the upper portion ofthe column, compressing the ethylene stream and effecting a temperature rise to the order of 100 to 150 F., passing the hot compressed gas in indirect heat exchange with a cooling medium, subsequently passing the partially cooled stream in indirect heat exchange with Vthe liquid phase in the lower portion ofY the separating and fractionating zone and effecting condensation of an appreciable part of the ethylene stream while supplying heat for reboiling WithinV the lower portion of the fractionating zone, subsequently effecting a pressure reduction of a cooled and condensed ethylene stream and passing the resulting cold stream to a receiving zone maintained at a reduced pressure whereby to .eifect the cooling of the latter stream to a temperature. below F., withdrawing a portion of the resulting substantially pure ethylene stream from the lower portion of the receiving Zone and passing it in heat exchange relationship with the mixed stream being introduced to the separating Zone as hereinbefore described, and'returning at least a portion of the substantially pure and cold ethylene stream to the upper end of the fractionating and separating zone as the aforesaid reflux stream.

In a preferable operation, suitable for effecting the greatest economy, the feed stream is cooled to the order of 20 F. and introduced at a pressure of the order of 200 p. s. i. g., while the subsequent compression and` condensing of 4 ing and operating costs. Further relatively high level cooling of the product stream is effected in the heat exchange chamber or reboiler connecting with the lower portion of the fractionating column, while the further pressure reduction upon entering the ethylene receiver, provides the desiredv low temperature stream. The resulting ethylene stream at' the receiver is preferably of the order of 20 F. and about 250 p. s. i. g. The product stream at this temperature and pressure is thus sucient to provide the desired'cooling of the charge streamrbeing introduced to the fractionating and separating column, as well as provide a cold reflux stream to the upper portion of the column, which upon further reduction'in pressure, to the order of 200 p. s. i. g., effects Yajdesired low temperature reflux.

The ethane stream withdrawn from the lower portion of the separating column, may also, if desired, be passed in heat exchange relationship with the charge stream to the fractionating column in order to provide in conjunction with the ethylene product stream the desired cooling of the charge stream to an introduction temperature of the order of 20 F. f v

In another specific embodiment of the present invention, the improvedy method of fractionation may be utilized fork theseparation and recovery of propylene from a binary mixture of propane and propylene, with the steps comprising passing the charge mixture in a heat exchange relationship if desired with at least a portion of the resulting separated component' streams-and effecting-a cooling of the mixture to a temperature below about 15 F., subsequently introducing the y cooled mixture at aV pressure of less than the ethylene stream is'geifected at a pressure of i the order of v55() to 600,p. s .i. g. to provide a temperature after compression of the order of 100-150f F. as hereinbefore noted.A Y

The external coolingprovided after the cornpression of the product stream is preferably provided by a refrigerant type of medium capable of being handled in a conventional heat exchanger and suitable to reduce the temperature of the compressed stream from about 150 F. to about 60 F., thus the greater amount of the net cooling is effectedat a relatively high level where greater cooling efficiency is obtainable, with an'accompanying reduction incool-V 1100 p. s. i. g. to a fractionating and separating zone and fractionating the mixture in the presence of a cold reflux stream of propylene obtained as hereinafter described, discharging propane from the lower portion 'of the zone and withdrawing a propylenefstream from the upper portion thereof,'compr'essing the latter stream to a superatmospheric pressure sufficient to elevate the temperature ofthe stream to a temperature of from 535 F. to 50 F., passing the compressed strearnin indirect heat exchange with a liquid phasein the lower portion -ofthe fractionating zone and reboiling the latter while simultaneously cooling and condensing the propylene stream, passing the condensed propylene stream to a receiving zone maintained at a reduced pressure and eifectingvthe cooling of the propylene to a temperaturebelow` 15 F., and withdrawing the resulting substantially pure propylene stream from the lower portion'ofthe receiving zone and returning at least a portion thereof to the fractionating zone as the aforesaid reflux stream.

Preferably, in a propylene-propane separation, the fractionating column is maintained at a superatmospheric pressure of the order of'about 50 p. s. i. g. andthe feed mixture is introduced to the column at a temperature of about5 F. A relatively high reflux to feedl ratio is maintained ofthe'order of aboutfl :tolfa'nd the reflux temperature is of. thel order ofv about 0 F.,whereby the overheadpropylenepassing tothe compressor is at abo'ut'O' F., while the'propa'ne being withdrawn froml the lower end of the fractionating maar ature after compression of the order ofV 35 F. to 50 F., permitting condensation by indirect heat exchange in the reboiler to the liquid in the lower portion of the ir'actionating` column. A subsequent reductionl of the reux stream to the order ci 50 p. s. i. g. maintained inthe fractionating zone effects' the reduction of the temperature of the reux stream to the order of F.

The present improved process, utilizing lower 'than conventional pressures and temperatures for effecting the separation of the binary mix-4 tures, is of particular advantage in that the com pression heating or auto-refrigeration method being utilized permits higher thermodynamic eiliciencies.l However, excessively low temperatures Within the fractionating column, that is temperatures within the range of deep-refrigeration, would require the necessityr of alloy metals and eliminate the present use of carbon steel for the fractionating column as well as for other portions of the unit. t is of coursey necessary ordesirable to carry out the conventional,` as well as the present improved operation, on a` substantially dry charge stream because of the below ireezling temperature range.

Reference to the accompanying drawing will serve to further clarify the novel operation and flow of the present invention, while. the explanation and description thereof will indicate addi tional features and advantages obtained b'y this `method of separation.

In order to make more understandable the operation and now of the present improved frac-` tionating process, it will be assumed that an ethane-ethylehe mixture is being charged to the fractionating unit for the recovery' ofv a desired ethylene fraction. Referring now to the drawing, a charge stream of the thane-ethylene mixture passes through line l. in accordance with apreferred operation, at a pressure ofi the order of 200 p.` s. i. g. and is cooled within-` the heat exchangers 2 and 3` so that the mixture is introduced into the fractionating' column. 4- through the feed line 5 at a low temperature of the order of 20o F. As indicated diagrammatically, the feed stream is split betweenA the two heat exchangers 2 and 3, a portion of the. feed' stream being cooled by a product stream4 or ethylene which is charged to the heaty exchanger 2 by way of line E and subsequently discharged therefrom by way of line 1l, while: an ethane stream recovered from the lower end of 'column 4 is charged to theV heat exchanger 3. by way of line` 8 andxsubsequently removed therefrom by way of line` 9. Itis thus seen that the resulting product streams are utilized to cool the charge` stream of ethane and ethylene prior to their introduction into: the column 4'. In the present.embodiment,l theoverhead product condensation: is provided for intermediate liquid storage. However, it ino storage is necessarytheethylene. may be `produced as agas.

The iractionatingV column.. 4 may be afconvehtional vertically disposed vessel having suitable bubble decks; or tray's spaced` throughout its height to eect a desired substantiallyA clean separation between the ethylene and ethane components being charged through the column.` The column is maintainediata superatmosphericpresL- sure of the order of 200 p. s'. irga- 'with'. aI bottoms temperature of the order of 07' Fi andlatop temperature of. the order of 35 F.: The ethyleneethane separationpis. carried out. in the presence' off a. renux stream. of: substantially' pure: liquid ethylenechargedstu.` the.` upper. lend oithe: column by way of une ru having control valve il; the" redux stream being supplied as a portion of the product stream, asv will be subsequently pointed out. The net overhead stream of ethylene. vapor is withdrawn by way of line I2 having control valve I3 and passed to a suitable suction. drum I4. The vapor stream subsequently passes by way of line i5 to compressor I6 which serves to raise thepressure thereof from. 200 p. s. i. g. to a high superatmospheric pressure of the order of 550 to 600 p. s. i. g.v The ethylene stream with heat of compression passes from the compressor i6 by way of line f1 to a suitable heat exchanger or cooler I8 supplied with a suitable cooling medium, preferably a refrigerant. Although not indicated in the drawing, a stage of water coolingmayV beV utilized prior to passing the liquefied stream to the exchanger 8 as there will normally be some excess heat in this operation. The heat of' compression raises the temperature of the product stream passing in line I1 to a temperature of the order of F. to 150` F. The stream is partially cooled in exchanger I8 to a temperature of the order of' 60 F". and is passed therefrom to the reboiler section by way of line |9`.

A portion of theI remaining heat of compression and condensation is utilized to supply heat and reboil the bottoms in the fractionati-ng column 4 with ethylene passing by way' of une 2in and valve 2l to the heat exchanger 2-2 for indirect heat exchange with the bottoms or' ethane being circulated through exchanger 22 by means ci lines 23 and 24. Where excess heatis available, a portion of the ethylene stream passes through line 25 and valve 2'6 to a refrigerant heat eX"- changer 21 so that additional heat may be: given up. Resulting cooledstreamsare withdrawnV from each of the exchangers by way" of' lines 23 and 2c, such that a combined streamA passes by way oi line 30 and control valve' 3i to an ethylene re'- ceiver 32.

The overhead product stream is thus used in a manner to supply heat from the heat of compression and condensation for reboiling the bottoms of the column while, subsequently upon reducing pressurey through valve 3* I there is pro vided a cold strean'i suitable to eiect, by means 'of' heatA exchange, a cooled charge stream to the fractionating column, and a cold redux stream charged to the topv of the column. In a normally designed plant, only one stage of compression is needed, with a compressor I`6- suitable to provide the desired high pressure stream and the desired flow through each of the process lines, the pressure from compression being such that all normally required pumps `and the like are elinii* hated.

In accordance with the preferred conditions of operation, the heat of compression is dissipated at a relatively high level, through the heat ex changers 1158, 22 and 2, so that the resulting stream charged to thereceiver by'w'ay of line 3i) i's'ata temperature of the order 4of 25' F. Pressure is then reduced "on` the liquid condensate upon its4 introduction intol the receiver 32, with valve 3|- serving as. aV `pressure reducing valve suitable to lower` pressure from the order of 550- 600 p. s. i. g..into the receiver `32 which is main'- tained at about 250 p. s. i. g.

Vaporized material resulting in the receiver 32 may be passed by way of' line 33 and valve 34 to line f5 which is in turn connected with the intake of the compressor I6. Thel liquid condensate is withdrawn from the lower end of the receiver by' Vway 4off `:line A35f.` and asi -hereinbefore noted, a portion thereof isv passed by way of lineA I and valve I I to the upper portion of the fractionating column 4 in order to provide a cold reux stream for the fractionation and separation within the column. The ethylene stream leaves thereceiver 32 at approximately 250 p. s. i. g. and a temperature of Y approximately 20 F., suchthat it enters the upper end of the column maintained at approximately 200 p. s. i. g., the reflux portion is still further cooled and the reflux enters the column at a temperature approximating a 35 F. temperature. Y

' The product stream is passed by way of line 35 and line 6 through a control valve 36, which is placed in the line at the inlet to the exchanger 2, and asrnoted hereinabove, the cold product stream furnishes a cooling medium for the charge mixture entering the unit by way of line l. Preferably, the product stream is reduced in pressure only a relatively small amount, from the order of 250 p. s. i. g. to approximately 200 p. s. i. g., or

to a slightly lower pressure if additional coolingV is required in the heat exchange operation. The resulting product stream which is discharged fromrexchanger 2 by way of line 'I may, if desired, be compressed prior to passing it to storage, or other suitable processing apparatus.V

The bottoms from the fractionating column 4 comprises a substantiallyrpure ethane stream, and as noted hereinafter, it is continuously withdrawn from the lower end of the column at a Y temperature of about 0 F. and at the column pressure of the order of 200 p. s. i. g. The stream passes by way of line 8 and'control valve 31, through heat exchanger 3 in indirect heat exchange Vwith a portion of the mixed charge stream. Where the present separation and recovery operation is utilized in connection with a unit providing a preliminary separation of the ethane and ethylene components from a mixed stream, such as a hypersorption unit, then substantially all of the ethane stream may be returned as recycle to a reaction zone, the effluent from which is charged to the hypersorption unit.

While the present operation is of particular advantage over the higher pressure fractionation process normally utilizedV with ethane-ethylene separation, there is a certain amount of net cooling which it is desirable to maintain available in order to insure proper removal of heat of compression as well as insure a balanced system. In this unit, a refrigerant is indicated as being used in heat exchanges I8 and 27, and while it is not intended to limit the type of refrigerant to any one compound or mixture, propane, ammonia or the like, may well be used and maintained in a closed system. The refrigerant is compressed in a suitable compressor indicated at 4U, and is discharged therefrom byV way of line 4I having control valve 62, which in turn discharges the material into a suitable refrigerant receiver 43.5 Condensed refrigerant leaves the lower portion of receiver 43 by way of line 44, from which a portion thereof is passed through a pressure reducing valve 45 to heat exchanger 2l, and another portion thereof passed by way of line 4B and a pressure reducing valve d1 to a heat exchanger I8.

aardgas Resulting vaporized streams are removed from be vented intol the compressorsuction line 49 and thereby returned to the refrigeration system.

In order to furtherl point out the advantage of the present operation, it may be noted that the refrigerant is utilized to lower the temperature of the compressed product streamV passing by Way of line Il and heat exchanger I8, from a relatively high level temperature of the order of F. to approximately 60 F., as well as to provide in conjunction with the reboiler 32 additional cooling that may be utilized to reduce the temperature of the net product stream to the order of approximately 25 F. prior to its introduction into the ethylene receiver 32 at a reduced pressure. The net cooling necessary is substantially less than that lin a conventional operation which utilizes ay refrigerant at the top of an ethylene separation column,V where reflux must be condensed by the use of a cold refrigerant. Two stages of compression generally are necessary to effect the desired cooling, with temperatures of the order of f20 F. or lower required, such that a cooling water is ofrelatively no utility or advantage. The presentrefrigeration system with compressor 40 is indicated as a single stage operation. However, where it is desired for purposes of economy, a two-stage refrigeration arrangement may be utilized, one-stage 0f compression connecting with the outlet from one exchanger such as exchanger I8, while another stage of compression takes suction from the other exchanger 2l, with the rst stage of compression combining with a second stage in a manner to reduce pressure requirements.

It may be again pointed out that the present operation is of advantage and provides a particularly economical operation, in that the compression of the overhead product stream provides heat which is utilized at the reboiler 32 and at the same time'perrnits an integral refrigeration operation wherein the product is lowered in temperature for pre-cooling the charge stream and for production of a cold reux stream. Where the fractionating column is maintained at a pressure substantially above the 200 p. s. i. g. pressure, say 250 p. s. i. g. or higher, it then becomes impractical and at higher pressures impossible to utilize the presentl arrangement where compression can be utilized for reboiling and condensing a large part of the reflux requirements.

' Where a pressure of less than 200 p. s. i. g. is utilized in the fractionating column 4, for ethylene separation then there is theoretically a further reduction in reflux requirements, as Well as a possible reduction in the size and diameter of the column itself; however, the 200 p. s. i. g. limit provides a practical range, in that the lower pressure and lower temperatures approaching deep refrigeration would require the use of alloys in the column itself, as well as Vin all connecting equipment. '.hus,` the use of expensive alloys and other contingencies encountered in substantially lower temperatures for the refrigeration cycle more than offset any possible advantages which may be obtained with going to a lower pressure within'the separating column. While the accompanying drawing provides a diagrammatic flow and method of operation, it

should be understood that the process is notV limited to an ethylene-ethane separation, for it is equally applicable to other homologue and isomer separationspsuch as the aforementioned propylene-propane separation and the like. It should also be understood that it is not intended to limit the invention to `the exact diagram Which has creaties@ rbeerrshowm tvithirespect tofthezphysicaliarrange r r fment, or asi to relative :rsizes or. equipment rand the like. Further, while the .foregoing itemp'eratures and' `pressures provide the approximate 'range for carrying out a preferred operation, it should be understood that `in any fractionating ``unit' of this typef reasonable-and minor variations 'in temperature and pressure may beutilized to effect aneiicient and uniform recovery unit. The

principal advantage of the present improved'` method of operation or'iiow 'is obtained through lthe use i of 'the compression "heating and autothermicfrefrigeration, `that "is, compressing Lthe overhead stream sufficiently i to 4permit lhigh-level cooling and condensation;orpartial condensation within a reboiler utilized to effect heating in the fractionating columnas well as the utilization or ahigh reflux ratio of a v"cooled" stream of a portion of the product stream, which is returned to the upper end of the fractionating zone.

I claim as my invention:

l. An improved method of separating and recovering fractions having a low relative volatility from a binary mixture, which comprises, cooling said mixture and subsequently introducing the cooled mixture at a relatively low fractionating pressure to a fractional-,ing and separating zone, fractienating said mixture in said zone in the presence of a cold reiiux stream of the lower boiling fraction which is obtained as hereinafter de- Y scribed, discharging the higher boiling fraction from the lower portion of the fractionating zone, withdrawing a stream of the lower boiling fraction from the upper portion of said fractionating zone, compressing the latter fraction to a substantially higher superatmospheric pressure and eifecting the heating thereof, passing the resulting compressed stream in indirect heat exchange with the liquid phase in the lower portion of the fractionating zone and reboiling liquid therein while simultaneously cooling and condensing the compressed stream, reducing the pressure on the resulting condensed stream of the desired lighter fraction to effect a further temperature reduction and introducing the same to a receiving Zone maintained at the reduced pressure and therein separating gas from liquid, withdrawing resulting substantially pure liquid fraction from the lower portion of the receiving Zone and returning a portion thereof to the fractionating and separating sone as said reflux stream and passing another portion thereof in indirect heat exchange with said mixture undergoing cooling as aforesaid.

2. The fractionating method of claim l further characterised in that said binary mixture is an ethylene-ethane mixture with the ethylene comprising the lower boiling fraction and the ethane comprising the higher boiling fraction, said binar5T mixture is charged to the fractionating zone at la temperature below 0 F., and at a pressure at less than 300 p. s. i. g., the ethylene fraction being withdrawn. from the upper portion of the Ifractionating column is compressed to a substantially high superatmospheric pressure sufficient to effect the heating of the stream to a temperature lof the order of 100 to 150 F., and the resulting partially condensed ethylene stream obtained after the indirect heat exchange with the liquid fraction in the lower portion of the fractionating Zone is reduced in pressure in the receiving Zone sufficiently to effect the cooling of the ethylene stream to a temperature below 0 F.

3. The improved method of claim 1 further .characterized in that y said binary mixture is a ""propvlene-propane mixture lwith the lower boiling fracticnabeing propylene'aiidth'e higherfboil- .L ing fraction being .propane, f the' mixture is f intric- -duced i to'l the` fractionatingfzonelat la temperature below F. and thefractionatingfzorie ismaintained atll a pressure off lessE than 1 Oflpfsniagf., the lowler boiling z-.propylene stre'am being withdrawn vfrom .the upper portion of thefractio'natingfzone is Acompressed nto "a substantially high "supera-tmospheric pressure sufficient to -eiect fr.the hea-ting of the stream to a temperatureof the order of `35 :F.to 50 l5.,andthe partially'cooled propylene 'stream resulting from rthe indirect 'heat exchange Vwith 'a liquidin ythevlower portion'of the lfractionatin'g column :is freduced `in pressure in the receiving zonesuiliciently to "effect `the i cooling of fthe ipropylene to 'a temperature below `l5"- F.

14. `An improved Amethod for, Vrecovering 'ethylene from an ethylene-ethane mixture which comprises, cooling said mixture to a temperature of about -20 F., subsequently introducing said cooled mixture at a pressure of the order of 200 p. s. i. g. to a fractionating and separating zone and fractionatng said mixture therein in the presence of a cold reflux stream of ethylene obtained as hereinafter described, discharging ethane from the lower portion of said zone and withdrawing a-n ethylene stream from the upper portion thereof, compressing the latter stream to a superatmospheric pressure of the order of 500 to 600 p. s. i. g. and effecting the heating of said stream to a temperature of the order of F. to F., passing said compressed stream in indirect heat exchange with a liquid phase in the lower portion of said fractionating zone and reboiling the latter while simultaneously cooling and condensing said ethylene stream, passing the resulting condensed ethylene stream to a receiving zone maintained at a reduced pressure of the order of 250 p. s. i. g. and effecting the cooling of said stream to a temperature of the order of 20 F., separating gas from liquid in. the receiving zone and withdrawing a resulting substantially pure liquid ethylene stream from the lower portion of said receiving zone, and returning at least a portion of the liquid ethylene stream to said separating Zone as aforesaid reflux stream.

5. The method of claim 4 further characterized in that at least a portion of the ethane separated and withdrawn from the lower end of the fractionating and separating zone is passed in heat exchange relationship with said mixture being introduced into the separating zone, whereby to effect with said ethylene stream the cooling of said mixture to said low temperature of the order of 20 F.

6. An improved method for recovering propylene from a propane-propylene mixture which comprises, cooling said mixture to a temperature of the order of 015 F., subsequently introducing said cooled mixture at a pressure of the order of 50 p. s. i. g. to a fractionating and separating zone and fractionating said mixture therein in the presence of a cold reflux stream of propylene obtained as hereinafter described, discharging propane from the lower portion of said zone and withdrawing a propylene stream from the upper portion thereof, compressing the latter stream to a superatmospheric pressure of the order of 100 p. s. i. g. and effecting the heating of said stream to a temperature of the order of 3040 F., passing said compressed stream in indirect heat exchange with a liquid phase in the lower portion of said fractionating zone and reboiling the latter while simultaneously coolingand condensing ing zone is compressed.

sequently withdrawing a resulting substantially pure liquid propylene stream from the lower portion of said receiving zone, and returning at least a portion of the liquid propylene stream toV said separating zone as aforesaid reux stream.

7. The process of claim 6 further characterized in that the ratio of said propylene reux stream being returned to said ractionating zone with respect to said mixture being introduced thereto is a ratio of the order 7 to 1.

8. The method of claim 1 further characterized in that separated gas is Withdrawn from the upper portion of said receiving zone and supplied to the compressing step wherein the lower boiling fraction frm the upper portion of the fractionat- JAMIES E. GANTT.

REFERENCES CITED The following references are of record in the file of this patent:`

UNITED STATES PATENTS Number Name Date 1,449,291 Mewes et al. Mar. 20, 1923 2,127,004 .Nelson Aug. 16, 1938 2,270,852 Schuftan Jan. 27, 1942 FOREIGN PATENTS Number Country Date 561,310 Germany Oct. 13, 1932 

1. AN IMPROVED METHOD OF SEPARATING AND RECOVERING FRACTIONS HAVING A LOW RELATIVE VOLATILITY FROM A BINARY MIXTURE, WHICH COMPRISES, COOLING SAID MIXTURE AND SUBSEQUENTLY INTRODUCING THE COOLED MIXTURE AT A RELATIVELY LOW FRACTIONATING PRESSURE TO A FRACTIONATING AND SEPARATING ZONE, FRACTIONATING SAID MIXTURE IN SAID ZONE IN THE PRESENCE OF A COLD REFLUX STREAM OF THE LOWER BOILING FRACTION WHICH IS OBTAINED AS HEREINAFTER DESCRIBED, DISCHARGING THE HIGHER BOILING FRACTION FROM THE LOWER PORTION OF THE FRACTIONATING ZONE, WITHDRAWING A STREAM OF THE LOWER BOILING FRACTION FROM THE UPPER PORTION OF SAID FRACTIONATING ZONE, COMPRESSING THE LATTER FRACTION TO SUBSTANTIALLY HIGHER SUPERATMOSPHERIC PRESSURE AND EFFECTING THE HEATING THEREOF, PASSING THE RESULTING COMPRESSED STREAM IN INDIRECT HEAT EXCHANGE WITH THE LIQUID PHASE IN THE LOWER PORTION OF THE FRACTIONATING ZONE AND REBOILING LIQUID THEREIN WHILE SIMULTANEOUSLY COOLING AND CONDENSING THE COMPRESSED STREAM, REDUCING THE PRESSURE ON THE RESULTING CONDENSED STREAM OF THE DESIRED LIGHTER FRACTION TO EFFECT A FURTHER TEMPERATURE REDUCTION AND INTRODUCTING THE SAME TO A RECEIVING ZONE MAINTAINED AT THE REDUCED PRESSURE AND THEREIN SEPARATING GAS FROM LIQUID, WITHDRAWING RESULTING SUBSTANTIALLY PURE LIQUID FRACTION FROM THE LOWER PORTION OF THE RECEIVING ZONE AND RETURNING A PORTION THEREOF TO THE FRACTIONATING AND SEPARATING ZONE AS SAID REFLUX STREAM AND PASSING ANOTHER PORTION THEREOF IN INDIRECT HEAT EXCHANGE WITH SAID MIXTURE UNDERGOING COOLING AS AFORESAID. 